广州市居民家庭室内灰尘中传统和新型阻燃剂与塑化剂的污染特征及健康风险评估

近年来,随着阻燃剂多溴联苯醚（PBDEs）和以邻苯二甲酸酯（PAEs）为代表的传统型塑化剂（LPs）的逐步禁用或限用,有机磷系阻燃剂（PFRs）等新型阻燃剂及替代型塑化剂（APs）的生产和使用呈逐年增长的趋势,其环境污染特征和人体暴露健康风险值得引起广泛关注. 目前,灰尘已广泛用于室内环境中PBDEs、PFRs和LPs等半挥发性有机污染物（SVOCs）的污染特征评估,而关于室内灰尘中APs的污染特征则鲜有报道.本研究以广州市42户普通居民家庭为研究对象,采集家庭室内灰尘并分析了PFRs、PBDEs、LPs和APs的含量及组成特征.结果表明,PFRs、PBDEs、LPs和APs在室内灰尘中均有广泛检出,其含量分别为593.28~11531.56、13.45~27029.13、40494.83~1154497.16和15365.19~1013352.51 ng·g^-1.大多数家庭中,PFRs和部分APs在灰尘中的含量呈现高于PBDEs和LPs的特征,PFRs和APs等新型污染物的人体暴露健康风险需引起高度关注.采用暴露模型评估人体经灰尘摄入和皮肤接触对目标污染物的日均暴露量,结果表明,幼儿对PFRs、PBDEs、LPs和APs的暴露量分别为6.488、1.425、854.009和433.922 ng·kg^-1·d^-1,成人的暴露量分别为0.403、0.091、54.239和27.557 ng·kg^-1·d^-1.进一步使用危险熵进行健康风险评价,结果显示,4类污染物对幼儿和成人的健康风险均在可接受范围内.     

四种环境雌激素对斑马鱼内脏团抗氧化防御系统的影响研究——17B-雌二醇与三种增塑剂DMP、DBP、DOP的影响

以斑马鱼(Danio rerio)为受试动物,研究了四种环境雌激素-17β-雌二醇(E2)和三种增塑剂(DMP、DBP、DOP)对其内脏团的氧化损伤及应激效应。经急性毒性实验,得到E2、DMP、DBP、DOP对成体斑马鱼96 h的半数致死浓度(LC50)分别为2.51、12.33、9.67、9.89 mg·L-1。在此基础上分别设置5个浓度梯度,研究E2(暴露2 d,4 d)、DMP、DBP、DOP(暴露4 d)对斑马鱼内脏团的超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、谷胱甘肽硫转移酶(GST)活性以及丙二醛(MDA)含量的影响。结果表明,SOD、CAT、GST、MDA对这四种环境激素都非常敏感,其中SOD、CAT、GST活性的影响均呈现先诱导后抑制的趋势,而MDA含量则随着污染物浓度的升高而增加。高浓度暴露条件下,E2(0.4 mg·L-1)和DMP、DBP、DOP(0.8 mg·L-1)对SOD、CAT、GST活性均有显著抑制(p0.05),MDA的含量有显著升高(p0.05)。可见,E2、DMP、DBP、DOP会导致斑马鱼内脏团氧化损伤,并且在同等浓度下E2的毒性明显高于三种增塑剂。     

Processing and Physical Properties of Plastics Made from Soy Protein Polyester Blends

Blending soy protein with polyesters using a polyvinyllactam as a compatibilizer successfully made soy protein-based plastics. The polyesters used to produce blends included polycaprolactone (PCL) and Biomax (a commercial biodegradable polyester). The blends were processed by compounding extrusion and injection molding. Blends containing soy protein/Biomax-poly(vinyl alcohol) had tensile strengths ranging from 16–22 MPa, with samples containing larger percentages of the synthetic polymer exhibiting greater strengths. Blends made from soy protein, Biomax, and PCL had tensile strengths ranging from 27–33 MPa. All the blends had high Young's moduli but demonstrated brittle characteristics as evident from their low elongations at break, ranging from 1.8–3.1%. Plastics made from soy protein/polyester blends exhibited low water absorption and had good stability under ambient conditions relative to the plastics made from soy protein alone. Blends made from soy protein flour produced plastics with the lowest water absorption.     

广州地区室内灰尘中典型非邻苯增塑剂的污染特征与暴露风险

非邻-苯二甲酸酯增塑剂作为邻-苯二甲酸酯的替代物被广泛用于生产和生活用品中,但目前对其环境存在和人体暴露风险知之甚少.为研究室内环境的污染状况及人体暴露,分析了广州市83户住宅灰尘中12种典型非邻苯增塑剂.结果表明,对-苯二甲酸二辛酯（DEHT）、偏苯三酸三辛酯（TOTM）、乙酰柠檬酸三丁酯（ATBC）、己二酸庚基壬基酯、己二酸二（2-乙基己基）酯和偏苯三酸三辛烷基酯100%检出.非邻-苯二甲酸酯增塑剂总含量中值为101 μg·g^-1,含量范围为22.4~615 μg·g^-1.DEHT的含量最高（含量范围9~487 μg·g^-1）,其次是TOTM （含量范围0.3~87 μg·g^-1）和ATBC （含量范围1.7~50 μg·g^-1）.通过暴露模型评估了成人与儿童经灰尘摄食的日暴露量,其中儿童摄入的非邻苯增塑剂总日暴露量为367 ng·（kg·d）^-1,是成人日暴露量43 ng·（kg·d）^-1的8~9倍.进一步通过危险商对暴露量进行风险评价,结果表明成人和儿童经灰尘摄食对非邻苯增塑剂的暴露风险均处于可接受范围.     

Biochemical Cooperation Between Klebsiella oxytoca Sc and Methylobacterium mesophilium Sr for Complete Degradation of Dimethyl Isophthalate

Klebsiella oxytoca Sc and Methylobacterium mesophilicum Sr were isolated from enrichment cultures using dimethyl isophthalate (DMI) as the sole carbon and energy source and mangrove sediment as an inoculum. Complete degradation of DMI required both species of bacteria at different biochemical transformation steps. The biochemical degradation pathway was DMI to monomethyl isophthalate (MMI) by K. oxytoca Sc, MMI to isophthalate (IPA) by M. mesophilium Sr, and IPA by both K. oxytoca Sc and M. mesophilium Sr sequentially. The consortium comprising of K. oxytoca Sc and M. mesophilicum Sr was effective in complete degradation of DMI in eight days. Our results suggest that a consortium of microorganisms indigenous to the mangrove environment is responsible for mineralization of environmental pollutant DMI through biochemical cooperation.     

Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain)

A monitoring programme was carried out on wastewater, surface and drinking water on the NW area of Spain during the four seasons of a year period (November 2007-September 2008). This study covered a series of emerging pollutants of different classes, including pharmaceuticals, neutral and acidic organophosphorus flame retardant/plasticizers (OPs), triclosan, phenoxy-herbicides, insect repellents and UV filters. From the total set of 53 compounds, 19 were found in raw wastewater with median concentrations higher than 0.1 μg L⁻¹. Among them, salicylic acid, ibuprofen and the UV filter benzophenone-4 (BP-4) were the most concentrated, exceeding the 1 μg L⁻¹ median value. Subsequently, 11 of these contaminants are not efficiently enough removed in the small WWTPs tested and their median concentrations in effluents still surpassed the 0.1 μg L⁻¹, so that they can spread through surface water. These chemicals are the pharmaceuticals naproxen, diclofenac and atenolol; the OPs tri(2-chloroethyl) phosphate (TCEP), tri(chloropropyl) phosphate (TCPP), tri-n-butyl phosphate (TnBP), diphenyl phosphate (DPhP) and diethylhexyl phosphate (DEHP); and the sulphonate UV filters BP-4 and 2-phenylbenzimidazole-5-sulphonic acid (PBSA). These OPs were then the dominant emerging pollutants occurring in surface and drinking water, where they are detected in the 20-200 ng L⁻¹ range. Pharmaceuticals and UV filters are typically below the 10 ng L⁻¹ level. Finally, herbicides were only detected in the last sampling campaign under the 100 ng L⁻¹ drinking water European Union limit.     

邻苯二甲酸二(异)丁酯及其替代品的内分泌干扰效应研究进展

邻苯二甲酸二丁酯(di-n-butyl phthalate, DnBP)和邻苯二甲酸二异丁酯(diisobutyl phthalate, DiBP)是广泛用于塑料、树脂和橡胶制品中的邻苯二甲酸酯类增塑剂,曾在各种环境介质中频繁检出.现有研究表明,DnBP和DiBP对人类和其他动物具有显著的内分泌干扰效应以及生殖发育毒性等不良影响,因而在许多国家和地区被限制使用,由此市面上涌现出了一些替代品增塑剂.本文结合国内外关于DnBP和DiBP及其替代品的研究成果,综述了DnBP和DiBP在个体、细胞和分子水平上的内分泌干扰效应与机制以及在市场应用中的替代情况,并且选取了4种典型的替代品(邻苯二甲酸二异壬酯、环己烷-1,2-二羧酸二异壬酯、二苯甲酸二聚丙二醇酯、三乙酸甘油酯)对其内分泌干扰效应进行对比分析.研究结果表明,DnBP和DiBP在环境低浓度下能够影响类固醇激素合成通路中关键基因的表达,进而改变生物体内类固醇激素的水平,高浓度暴露时则会对生殖器官造成损伤并最终降低生殖能力,妊娠期暴露还会对后代产生相同的影响.DnBP和DiBP的4种替代品在急性毒性、持久性和生物可累积性方面均有所降低,内分泌干扰效应也显著降低,但缺乏系统的研究以全面评估其可替代性.提出今后替代品的安全性评估应纳入更多的毒性终点并深入研究相关的毒性效应机制,以保证替代化学品的安全性.     

Concentrations of phthalate esters and identification of other additives in PVC children’s toys

This study was intended to provide data on the composition of soft PVC toys, addressing the widest practicable range of chemical additives and including non-phthalate additives. The study also included toys from as many countries as possible, since for many, no data were available. A total of 72 toys were purchased in 17 countries. The majority (64) were PVC or had PVC sections. In almost all the soft PVC toys analysed, phthalates comprised a sizeable proportion (most frequently 10–40%) of the total weight of the toy. The predominant phthalates detected were diisononyl phthalate (DINP) and di(2-ethylhexyl) phthalate (DEHP). Other phthalates identified in high concentrations in some toys include isomeric mixes of diisooctyl phthalate (DIOP) and diisodecyl phthalate (DIDP). The estrogenic chemical nonylphenol was isolated from 13 toys, while 2 toys were found to contain the fungicide Fungitrol 11 (Folpet). 78% of PVC toys contained one or more extractable organic compounds in addition to those reported above. Some of these data have been released previously by Greenpeace and made available on the internet.This report, however, which is intended for a technically expert audience, has been peer reviewed and contains further analytical data that have not been published before.     

Chemical Compositions and Sources of Organic Matter in Fine Particles of Soils and Sands from the Vicinity of Kuwait City

Fine particles in the atmosphere from soil and sand resuspension contain a variety of organic compounds from natural biogenic and anthropogenic matter. Soil and sand samples from various sites near Kuwait city were collected, sieved to retain the fine particles, and extracted with a mixture of dichloromethane and methanol. The extracts were derivatized and analyzed by gas chromatography-mass spectrometry in order to characterize the chemical compositions and sources of the organic components. The major inputs of organic compounds were from both natural biogenic and anthropogenic sources in these samples. Vegetation was the major natural source of organic compounds and included n-alkanols, n-alkanoic acids, n-alkanes, sterols and triterpenoids. Saccharides had high concentrations (31–43%) in the sand dune and seafront samples, indicating sources from decomposed vegation materials and/or the presence of viable microbiota such as bacteria and fungi. Vehicular emission products, leakage of lubricating oils, discarded plastics and emissions from cooking operations were the major anthropogenic inputs in the samples from the urban areas. This input was mainly UCM, n-alkanes, hopanes, plasticizers and cholesterol, respectively.